CN105826528A - Porous silicon-copper composite material and preparation method and application thereof - Google Patents
Porous silicon-copper composite material and preparation method and application thereof Download PDFInfo
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- CN105826528A CN105826528A CN201610165059.5A CN201610165059A CN105826528A CN 105826528 A CN105826528 A CN 105826528A CN 201610165059 A CN201610165059 A CN 201610165059A CN 105826528 A CN105826528 A CN 105826528A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a porous silicon-copper composite material.The preparation method specifically comprises the steps that CuO powder and Mg2Si powder are mixed to be uniform to be subjected to heat treatment at the temperature of 600 DEG C-700 DEG C and then subjected to acid pickling and aftertreatment to obtain the porous silicon-copper composite material.According to the preparation method, the preparation technology is simple, the great operability is achieved, the adopted raw materials are rich in source and low in price, and the adopted method way is easily conducted in a factory; particularly, a replacement reaction of magnesium and copper oxide is ingeniously utilized, nano-scale copper particles are generated and uniformly dispersed on the surface of porous silicon while porous silicon is prepared, and the improvement role of copper on the conductivity of a whole material system and the buffer role of the copper particles on the size changes of silicon during extraction and insertion of lithium ions are more fully played.Through the potential method, the silicon-copper composite material with a unique structure can be massively synthesized.
Description
Technical field
The invention belongs to the preparation field of composite, be specifically related to a kind of porous silicon-carbon/carbon-copper composite material
And its preparation method and application.
Background technology
Lithium ion battery, is called for short lithium battery, is a kind of embedding utilizing lithium ion in positive and negative pole material
With the reversible secondary cell that abjection realizes charge and discharge.It because have that capacity is high, voltage platform high with
And the feature such as have extended cycle life and be widely used in various electronic product, hybrid vehicle and electronic vapour
In the fields such as car.As the energy storage mode of a kind of high-efficiency cleaning, lithium ion battery future for a long time in
Also has great application development space.
At present, the lithium ion battery negative material of commercialization mainly uses the carbon material with graphite as representative
Material.As lithium ion battery negative material, graphite only has the theoretical specific capacity of 372mAh/g, it is difficult to
Requirement to the lithium ion battery of height ratio capacity in meeting life and producing, therefore, research worker is more
Carry out the most sight and invest the height ratio capacity lithium ion battery negative material with silicon materials as representative.
When silicon is as lithium ion battery negative material, there is the theoretical specific capacity decupling material with carbon element
(4200mAh/g) with relatively low electrode potential, it is possible to meet height ratio capacity, high output voltage platform
The requirement of lithium ion battery.But, silicon with lithium alloyage during, by generation up to 400%
Volumetric expansion, this makes the negative pole of silicon produce continuous change in volume in battery charging and discharging circulates,
So that active substance ruptures, broken even with electrode delamination, finally make battery capacity acute
Strong decline.Additionally, due to the electric conductivity of silicon is not fine, electric transmission inefficient, also exist
Have impact on the performance of battery to a certain extent.
The problem being had as lithium ion battery negative material for above silicon, researcher both domestic and external
Devise various composite system silicon materials are improved.Wherein, silicon-composite copper material
Material system receives concern especially, this is because: on the one hand, copper has preferable mechanical performance,
Can effectively limit and buffer silicon change in volume in charge and discharge cycles；On the other hand, copper has excellent
Good electric conductivity, can be effectively improved the electron transport ability of negative material.
(Ning Wang, Tao Hang, Huiqin Ling, the Anmin Hu and Ming such as Ning Wang
Li.High-performance Si-based 3D Cu nanostructured electrode assembly for
Rechargeable lithium batteries.J.Mater.Chem.A, 2015,3,11912 11919) carry
Go out the first copper tapered array preparing growth in situ on copper sheet, spattered by magnetic control on its surface the most again
The method penetrated prepares one layer of silicon, obtains the copper-silicon laminated film of the nucleocapsid structure of tapered array pattern.
Although this method improves the cyclical stability of silicon, eliminate cathode size preparation and the work of coating
Sequence, but, the method for growth in situ copper tapered array is complicated, and repeatability is the highest, and magnetron sputtering
The cost of silicon is the highest, is not suitable for large-scale commercial application.
(Jungho Lee, Kei Hasegawa, Toshiyuki Momma, the Tetsuya such as Jungho Lee
Osaka,Suguru Noda.One-minute deposition of micrometre-thick porous
Si-Cu anodes with compositional gradients on Cu current collectors for lithium
Secondary batteries.Journal of Power Sources 286 (2015) 540e550) by Si, Cu
While heated to 2000 DEG C so that Si, Cu first evaporate in the copper sheet substrate being re-depositing on lower temperature.
Period, the boiling point that make use of Cu is relatively low, and vapour pressure is higher, has obtained the closer to substrate, Cu content
The highest porous Si-Cu laminated film with finite concentration gradient.Although this Si-Cu THIN COMPOSITE
Film has preferable cyclicity and high rate performance, but severe to the requirement of high temperature and vacuum in preparation process
Carve, it is difficult to quantify to produce.
Yong-Mook Kang etc. (Yong-Mook Kanga, Min-Sik Park, Min-Sang Song,
Jai-Young Lee.A relation between enhanced Li ion transfer and the
improvement in electrochemical performance of a Si–Cu–carbon composite.
Journal of Power Sources 162 (2006) 1,336 1340) utilize silica flour priority and copper and carbon
Mixing and ball milling, obtains Si-Cu-C composite powder material.Although this method is simple, and cost is relatively
Low, but its cyclical stability is unsatisfactory.
(Jungdon Suk, Do Youb Kim, Dong Wook Kim, the Yongku such as Jungdon Suk
Kang.Electrodeposited 3D porous silicon/copper films with excellent stability
and high rate performance for lithium-ion batteries.J.Mater.Chem.A,2014,2,
2478 2481) copper of way elder generation one layer of porous of electroplating deposition of plating, then same re-plating are used
One layer of silicon, obtains the copper-silicon laminated film of porous.The nucleocapsid structure shape of copper-silicon that this way obtains
Looks rule, composition is uniform, and the cycle performance of silicon and high rate performance also obtain a certain degree of raising, but
The way being plating is high to equipment requirements, and energy consumption is huge, is not suitable for large-scale commercial production.
Summary of the invention
The invention provides the preparation method of a kind of porous silicon-carbon/carbon-copper composite material, technique is simple, it is easy to
Repeat, large-scale industrial production can be realized.Porous silicon-the carbon/carbon-copper composite material prepared is not only
Specific surface area is very big, even aperture distribution, and copper exists with the form Dispersed precipitate of nano-scale particle
The surface of silicon, the buffering silicon change in volume when removal lithium embedded that can be just right also increases substantially body
The electric conductivity of system.It is applied in lithium ion battery as negative material using it, excellent performance will be obtained.
A kind of method preparing porous silicon-carbon/carbon-copper composite material, specifically includes following steps:
By CuO, Mg2Two kinds of powder materials of Si uniformly mix, and carry out heat treatment at 600～700 DEG C,
Described porous silicon-carbon/carbon-copper composite material is obtained again through pickling and post processing.
In the present invention, using magnesium silicide, copper oxide is raw material, at high temperature, make use of magnesium silicide high
The principles such as the displacement reaction that temperature is decomposed between silicon and magnesium, and magnesium and copper, in its product pickling processes
After, successfully synthesize porous silicon-carbon/carbon-copper composite material, can apply to lithium ion battery negative material.
The method is very simple, and operating process is easy, and the instrument and equipment of use is common to be easy to get, the raw material of employing
It is finished industrial product, easily realizes large-scale industrial production.It is to be obtained by the simple means of one
The method of the porous silicon-carbon/carbon-copper composite material of labyrinth.
As preferably, described CuO and Mg2The mass ratio of two kinds of powder body of Si is 0.5～2:1.
As preferably, the time of described heat treatment is 8～10h, is passed through argon conduct in heat treatment process
Protective atmosphere.
As preferably, the hydrochloric acid that described pickling uses concentration to be 0.1～5mol/L, the process time is
3～5h.
As preferably, described post processing includes that washing, product are centrifugal and are vacuum dried.Described water
Wash and deionized water can be used 3～5 times to clean, until solution reaches neutrality.
The invention also discloses the porous silicon-carbon/carbon-copper composite material prepared according to above-mentioned method, and
Application in lithium ion battery.
This patent make use of the displacement reaction of magnesium and copper oxide cleverly, preparing the same of porous silicon
Time, by by the magnesium uniform disperse of copper that obtains of displacement on the surface of silicon, obtain structure and composition uniformly divide
Porous silicon-the carbon/carbon-copper composite material of cloth.It is multiple that the ball-milling method usually used with this area researcher prepares copper-silicon
Condensation material is compared, and is possible not only to obtain the loose structure that structure is unique, and copper will not be agglomerated into bulk,
But with the form Dispersed precipitate of nano-scale particle in the surface of porous silicon, not only uniformity is more preferable, and
And can preferably play copper and to the raising effect of whole system electric conductivity and silicon volumetric expansion is delayed
Punching effect.
Compared with prior art, the present invention has a following useful technique effect:
1) present invention has prepared the porous silicon-copper composite powders material with unique texture, permissible
Effectively help solution silicon is as the problem existed during lithium ion battery negative material, this is because: first
First, substantial amounts of space in porous silicon, it is provided that the space of silicon volumetric expansion, reduce silicon grain and expand
Time mutually extrude and the probability that ruptures；Then, the copper being compounded in silicon face can also effectively limit silicon
Outside volumetric expansion, plays the effect of cushion.Secondly, copper has the electric conductivity of excellence, and this will
Improve the electric transmission efficiency of negative active core-shell material greatly.
2) present invention utilizes the displacement reaction between the thermal instability of magnesium silicide and metal, it is possible to
Obtain the porous silicon-carbon/carbon-copper composite material with unique texture.Preparation method is simple, raw material sources
Abundant and price inexpensively, is suitable for extensive commercial application.
Accompanying drawing explanation
Fig. 1 is the test data preparing product in embodiment 1；Wherein, figure a and figure b is that scanning electron microscope shines
Sheet (SEM), figure c is x-ray diffraction collection of illustrative plates (XRD), and figure d is x-ray probe power spectrum (EDS).
Fig. 2 is that the common porous silicon of the product prepared in embodiment 1 and comparative example 1 preparation is as negative pole material
The circulation volume curve of the lithium ion battery that material assembles and the comparison diagram of coulombic efficiency；Wherein, solid
For embodiment 1 is prepared the data point of product, the hollow data point for common porous silicon.
Fig. 3 is the test data preparing product in embodiment 2；Wherein, figure a and figure b is that scanning electron microscope shines
Sheet (SEM), figure c is x-ray diffraction collection of illustrative plates (XRD), and figure d is x-ray probe power spectrum (EDS).
Fig. 4 is that the common porous silicon of the product prepared in embodiment 2 and comparative example 1 preparation is as negative pole material
The circulation volume curve of the lithium ion battery that material assembles and the comparison diagram of coulombic efficiency；Wherein, solid
For embodiment 2 is prepared the data point of product, the hollow data point for common porous silicon.
Fig. 5 is the test data preparing product in embodiment 3；Wherein, figure a and figure b is that scanning electron microscope shines
Sheet (SEM), figure c is x-ray diffraction collection of illustrative plates (XRD), and figure d is x-ray probe power spectrum (EDS).
Fig. 6 is that the common porous silicon of the product prepared in embodiment 3 and comparative example 1 preparation is as negative pole material
The circulation volume curve of the lithium ion battery that material assembles and the comparison diagram of coulombic efficiency；Wherein, solid
For embodiment 3 is prepared the data point of product, the hollow data point for common porous silicon.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not
It is confined to following example.
Embodiment 1
1) by CuO, Mg2Si uniformly mixes for 2:1 in mass ratio.
2) by the raw material of mix homogeneously at 600 DEG C of heat treatment 10h, heat treatment process is in the protection of argon
Carry out under atmosphere.
3) by step 2) products therefrom processes 5h in certain density hydrochloric acid, and concentration of hydrochloric acid is 0.2
Mol/L, re-uses deionized water and cleans 3 times, be then centrifuged for after acid treatment, finally carry out vacuum and do
Dry.
The product that the present embodiment prepares is porous silicon-carbon/carbon-copper composite material, its pattern and structural characterization
As it is shown in figure 1, as shown in Figure 1, the granule of porous silicon-copper is about 2-10 μm, particle surface and interior
Portion is uniform-distribution with countless nano level hole, and the oeverall quality mark of copper is 47.1%, its mainly with
Elemental copper and molecular formula are Cu3Presented in the copper-silicon alloy of Si, and form nano level granule more
Dissipate the surface in silicon, form uniform silicon-copper compound system.
Porous silicon-the copper prepared by the present embodiment is made button cell and is carried out lithium electric performance test, and with
Porous silicon prepared by comparative example compares, and obtains the comparison diagram of circulation volume curve and coulombic efficiency.
As shown in Figure 2, although owing to copper does not has lithium electroactive so that the initial specific capacities of porous silicon-copper is slightly
Less than common porous silicon, but, after 30 circulate, its actual capacity is significantly larger than common
Porous silicon, has more excellent cycle performance.Therefore, this material system with unique texture
The advantage of performance is embodied clearly.
Comparative example 1
The preparation of common porous silicon, concretely comprises the following steps:
By magnesium silicide in air atmosphere in 600 DEG C of heat treatment 10h, dilute hydrochloric acid is then used to carry out acid
Washing, finally centrifugal drying obtains common porous silicon powder.
Embodiment 2
1) by CuO, Mg2Si uniformly mixes for 1:1 in mass ratio.
2) by the raw material of mix homogeneously at 650 DEG C of heat treatment 9h, heat treatment process is in the protection of argon
Carry out under atmosphere.
3) by step 2) products therefrom processes 4h in certain density hydrochloric acid and hydrofluoric acid solution,
Concentration of hydrochloric acid is 2.0 mol/L, re-uses deionized water and cleans 4 times, is then centrifuged for, finally carries out
Vacuum drying.
The present embodiment products therefrom is porous silicon-carbon/carbon-copper composite material, wherein, have Cu about half and
It is Cu that Si defines molecular formula3Copper-the silicon alloy of Si, the oeverall quality mark of copper is 34.6%.
Porous silicon-the copper prepared by the present embodiment is made button cell and is carried out lithium electric performance test, and with
Common porous silicon compares, and obtains the comparison diagram of circulation volume curve and coulombic efficiency.Can by Fig. 4
Know, although owing to copper does not has lithium electroactive so that the initial specific capacities of porous silicon-copper is the most common
Porous silicon, but, through 30 circulate after, its actual capacity is significantly larger than common porous silicon,
There is more excellent cycle performance.Therefore, this have the material system of unique texture to performance
Advantage embodies clearly.
Embodiment 3
1) by CuO, Mg2Si uniformly mixes for 1:1 in mass ratio.
2) by the raw material of mix homogeneously at 700 DEG C of heat treatment 8h, heat treatment process is in the protection of argon
Carry out under atmosphere.
3) by step 2) products therefrom processes 3h in certain density hydrochloric acid, and concentration of hydrochloric acid is 5
Mol/L, re-uses deionized water and cleans 5 times, be then centrifuged for, be finally vacuum dried.
The present embodiment products therefrom is porous silicon-carbon/carbon-copper composite material, wherein, and most Cu and Si
Defining molecular formula is Cu3Copper-the silicon alloy of Si, the oeverall quality mark of copper is 35.8%.
Porous silicon-the copper prepared by above-mentioned the present embodiment is made button cell and is carried out lithium electric performance test, and with
Common porous silicon compares, and obtains the comparison diagram of circulation volume curve and coulombic efficiency.Can by Fig. 6
Know, although owing to copper does not has lithium electroactive so that the initial specific capacities of porous silicon-copper is the most common
Porous silicon, but, through 30 circulate after, its actual capacity is significantly larger than common porous silicon,
There is more excellent cycle performance.Therefore, this have the material system of unique texture to performance
Advantage embodies clearly.
Claims (7)
1. the method preparing porous silicon-carbon/carbon-copper composite material, it is characterised in that step is as follows:
By CuO, Mg2Two kinds of powder materials of Si uniformly mix, and carry out heat treatment at 600～700 DEG C,
Described porous silicon-carbon/carbon-copper composite material is obtained again through pickling and post processing.
The method preparing porous silicon-carbon/carbon-copper composite material the most according to claim 1, its feature exists
In, described CuO and Mg2The mass ratio of two kinds of powder body of Si is 0.5～2:1.
The method preparing porous silicon-carbon/carbon-copper composite material the most according to claim 1, its feature exists
In, the time of described heat treatment is 8～10h, is passed through argon as protective atmosphere in heat treatment process.
The method preparing porous silicon-carbon/carbon-copper composite material the most according to claim 1, its feature exists
In, the hydrochloric acid that described pickling uses concentration to be 0.1～5mol/L, the process time is 3～5h.
The method preparing porous silicon-carbon/carbon-copper composite material the most according to claim 1, its feature exists
In, described post processing includes that washing, product are centrifugal and are vacuum dried.
6. porous silicon-carbon/carbon-copper composite material that prepared by a method according to claims 1 to 5.
7. porous silicon-carbon/carbon-copper composite material according to claim 6 is in lithium ion battery
Application.
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| CN106784613A (en) * | 2017-02-23 | 2017-05-31 | 华南理工大学 | A kind of porous silicon copper-plating electrode for lithium ion battery and preparation method thereof |
| CN107394150A (en) * | 2017-07-14 | 2017-11-24 | 东南大学 | A kind of mesoporous silicon copper composition electrode material and its preparation method and application |
| CN107742715A (en) * | 2017-10-25 | 2018-02-27 | 山东大学 | A kind of preparation method of lithium cell cathode material nano-structure porous silicon |
| CN115285998A (en) * | 2022-08-30 | 2022-11-04 | 山东大学 | Preparation method and application of three-dimensional porous Cu3Si @ Si lithium battery negative electrode material |
| WO2023124405A1 (en) * | 2021-12-28 | 2023-07-06 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material and preparation method therefor, and lithium ion battery |
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